Crude anthracene separation



Patented Mar. 23, 1 948 trick, Pittsburgh, Pa., assignors to Koppers Company, Inc., Pittsburgh, Pa., a corporation of Delaware Application February 1, 1945, Serial No. 575,686

9 Claims. 1

The present invention relates to the separation and purification of tar constituents and especially to the refining of anthracene.

In the commercial distillation of tar there is obtained a crude anthracene cut, a so-called anthracene-oil fraction, that is usually cooled,

The similarity has made it difiicult to separate and purify even the predominant constituents by the conventional processes such ascaustic fusion, vacuum distillation, and solvent extraction.

More recently, the crude anthracenes have lloeen hydrogenated for protracted periodsat high pressures (over 150 atmospheres) and at high "temperatures (over 400 0.), with and without catalysts, usually for the sole purpose of recoverin considerable cracking of the principal constituents, especially anthracene. cracking when operating without catalysts it is now considered better practice to hydrogenate for shorter periods (:1 hour).

carbazole. These conditions produced To reduce this When operating with catalysts at pressures above 100 atmospheres, somewhat lower temperatures, from about 300 C. upwards, have been used. Among the catalysts that have been employed are included the metals, metal sulphides, and difiicultly reducible metal oxides of such metals as nickel, cobalt, iron, molybdenum, chromium, tungsten, uranium, vanadium, copper, zinc, tin, manganese, and sodium. Under these conditions the major portion of the carbazole and phenanthrene content of the crude anthracene is not hydrogenated, whereas the anthracene is hydrogenated to various hydrides. The hydrogenated product is thereafter simply cooled and/or treated with solvents to separate first carbazole and then phenanthrene from the liquid hydrogenated anthracene portion. The hydrogenated anthracene is thereafter dehydrogenated and anthracene recovered therefrom. After further purification, the carbazole, phenanthrene, and anthracene obtained by such processes will each have a purity in the range of from 70% to 95%. The recovery of. each of these purified products will vary from about 25% to 60% of their original content in the crude anthracene.

'Studies in the hydrogenation of pure anthracene with some of the more active of the previously mentioned metal catalysts at atmospheric or slightly elevated pressures and temperatures upward of 150 0., and with the sulphides and oxides of these metals at temperatures upward of 300 0., and pressures'upward of atmospheres, show formation of various hydride's, among these being 9,10-dihydroanthracene, tetrahydroanthracene, octahydroanthracenes, and perhydroanthracene;

Very often, it has been shown that reactions taking place with ease with pure anthracene, carbazole, and phenanthrene do not take place as readily when crude products containing these constituents are similarly treated to separate them. It has now been found, however, that by retarded and controlled hydrogenation of even a very crude anthracene having only a relatively 10W content of the wanted products, that the anthracene present therein can be hydrogenated to yield predominantly only a single hydride, namely, 9,10-dihydroanthracene -with substantially no cracking. Furthermore, this hydride can be easily separated from the hydrogenated product and purified. This retardedandcontrolled hydrogenation is especially applicable to the refining of crude anthracene cake to recover carbazole, phenanthrene, and anthracene therefrom. V V r The primary object of the present invention is to provide a process for refining crude anthracene to obtain therefrom good yields of highly purified products.

A further object of invention is to provide a process for hydrogenating crude anthracene to obtain a high yield of high quality 9,10,-dihydroanthracene. I

Another object of invention is .to provide a process for separating 9,10-dihydroanthracene, phenanthrene, carbazole, and other minor. constituents as highly purified products from hydrogenated crude anthracene. g

Yet another object of invention is to provide a hydrogenation process with distillation and solvent extraction for separating constituents of crude anthracene... I

, Yet a further object of invention is to provide a process for producing highly purified anthraquinone from anthracene oil or distillates containing anthracene. H e

The invention has for further objects such other improvements and such other operative advantages or results as may befound to obtain other crude tar in the processes or apparatus ,hereinafter de scribed or claimed.

tionation and then solvent extraction steps for V separating and. purifying the constituents of a crude anthracene cake. The ,twofiow sheets and the inventions described therein are essentially the same. Each applies a distillation and a solvent extraction to the hydrogenated anthracene aes'ams catalytic activity by varying the time of treatment. V

It should be pointed out that an anthracene cake always contains sufficient sulphur products to convert the aforementioned metals, their oxidesand salts, such as the chlorides, phosphates, carbonates, etc., -to the metal sulphides under the proposed novel operating conditions. Thus, for purposes of the present invention, when hydrogenating crude anthracene cake, a metal sulphide hydrogenation catalyst may be employed which is preparedas su'chby known means, or the metal sulphide may be prepared in situ from the metals, their oxides vor their salts. I

Fo controlled hydrogenation, it is preferred to employ atemperature below 350 C. and within the range of 250 C. to 350 C. Pressures below cake. It is optional to solvent extract first (Fig.

1) or distill first (Fig. 2).

Referring to the flow sheet of Fig. 1, the crude anthracene from storageZ augmentedby material obtained from'a still 3111 a subsequent process .step, is transferred-to a conventional batch or to a continuous hydrogenation ,unit t and is therein mixed witha metalsulphide hydrogenation catalyst from-catalyst storage 6, the mixture being heated under the pressure of hydrogen from hydrogen storagelfiior a period sufficient to convert the anthracene. content of the mixture to 9,10-dihydroanthracene. can beany product containing anthracene in association with other impurities. Usually the crude anthracene comprises a fraction obtained in the distillation of tar, a fraction in the so-called anthracene. oil range, .This crude anthracene will als comprise .carbazole and phenanthrene with smallerconcentrations of the .homologs of anthracene and phenanthrene, acenap-hthene, fluorene, chrysene, and acridine. While the an- The crude anthracene thracene in .such a tar fraction can be selectively hydrogenatedit isusuallypreferred to concentrate theQanthracene', carbazole, and phenan threne into a so-called anthracene cake by cooling the tar fractionto solidify these high melting constituents,and ,then' to express orotherwise to remove the liquid iconstituents bysome type of filtration... .The resultingcake will comprise about 20%to 50% anthracene. The novel hydrogenation is applicable to any crude product containing anthracene. "The, subsequent. separation of constituentsfrom the hydrogenated product will depend on the chemical and physical properties of the constituents associatedwiththe anthracene or the 9,10 -dihydroanthracene. Y

The crude anthracene is mixed with anyone of the usual metal'sulphide hydrogenation catalysts such as the sulphide or sulphides of nickel, cobalt, molybdenum, chromium, manganese, tungsten, vanadium, tin, ,etc. have been employed for thehy'drogenationof coal-derived products, yet. for thepurpose of the present invention they are too active,.since they bring about unwanted hydrogenation ofthe carbazole and phenanthrene and convertv the wanted 9,10-dihydroanthracene to higher hydrides. On the .other hand, the action of the metal sulphide catalysts in general is mild and controllable. It is preferred to employ about 10% by weight of catalyst, the quantity beingvariable, for example,

the smaller the quantity of catalyst, the temperature and pressure being constant, the longer the time required to obtain comparable results. As

' betweenjthe variousmetalsulphide catalysts, it is usuallypossible to compensate ior variations 100 atmospheres, and preferably between 20 and 100 atmospheres have been found to retard the reaction beneficially and are most satisfactory for hydrogenating crude anthracene to 9,10-dihydroanthracene. Anumber of important benef ts are obtained by the use of these novel operating. conditions. Thus, a maximum conversion of the anthracene to QJO-dihydroanthracene is thereby achieved, with a minimum conversion thereof to the higher hydrides, regardless of the presence of other constituents in the crudeanthracene cake. The hydrogenation and/ or decomposition of carbazole and phenanthrenefare largely. elirni nated. Furthermore, hydrogenation periods in excess of the necessary hydrogenation time do not cause conversion of the vwanted 9,10,.- dihydroanthracene to unwanted, higher hydrides at these low pressures, contrary to the prior artexperience,

At median pressfures of from so tofiQ-atmos pheresfwithin the specified limits for temperature, and depending upon thetypeof catalyst, the catalyst concentration and theconcentration of other materials in the; crude anthracene,

the'preferred hydrogenation is usually. completed in from .4 to 6 hours. Thus, from an anthracene cake comprising 25 -to 30 anthraceneand under the above-mentioned conditions, about of the anthracene is obtained as arelatively pure 9,10-dihydroanthracene. 1 I

Under the preierredconditions of'tlrne, temperature catalyst, and. catalyst concentration, but at pressures over atmospheres, the ;9,-1 0- dihydroanthracene production is, reduced. lfhis compound, or perhapseven the anthracene, is converted; to higher hydrides, largely tetrahydroanthracene,-that are not oxidizable directly to anthraquinone .asris the 9-,l0 -di-hydroanthrac ene;

After the, hydrogenation step ,ofthe crude ;anthracene, the major constituents ofcthe hydrogenation product can be separated alternatively by process stepsthat begin with :a solventiextraction or with a fractionation step. :If the solvent extraction isused'first, the hydrogenation product is treated inanextractor Ill with:solvent from storage l2 thatselectively removes 'thei9;l0

methyhethyl, and isopropyl alcohols, cyclohexi ane and methyl cyclohexaneare excellent solvent-s. The treated mixture goesto a separator,

l4. that can'be a filter, a, centrifuge-or the lihe, the insoluble carbazole goin to a, oarbazoleextractor l6, whereas the solute is flowed to a frace tion-ator I78, to be distil ed, .preicrably at reduced 5. pressures to minimize the dehydrogenation of 9,10-dihdroanthracene to anthracene. Usually the separated fractions from a distillation are distributed as follows: solvent to solvent storage I2, forerunnings to storage 20, 9,10-dihydroanthrancene to storage 22, 70-85% phenanthrene to storage 24 and the still residue to storage 26. The forerunnings in 20 and the still residue in 26 can be blended with other tar fractions or accumulated for the separation therefrom of fluorene, acenaphthene, and the like. The purity of the phenanthrene can be raised by known methods, for example, by recrystallization from the above-named solvents. The crude carbazole in extractor Iii can be extracted, preferably with a heated aromatic solvent such as coal tar naphtha, xylene, pyridine, or the like, from solvent storage 28. The insoluble catalyst is first separated in a separator 30 and is then recycled for further use to catalyst storage 6. On cooling and crystallizing in a crystallizer 32, the purified carbazole crystals are separated from mother liquor in a separator 34, washed therein with the solvent from storage 28, and after drying in a dryer 36 go to storage 38, as carbazole having a purity of 90% to 95%. By repeatedly crystallizing this carbazole product as described it is possible to produce substantially pure carbazole. From the separator 34, the mother liquor containing anthracene, carbazole, 9,10-dihydroanthracene, etc., is distilled in still 3, the solvent therefrom being returned to solvent'storage 28, whereas the residue is recycled to crude anthracene storage 2 for reworking.

. The 9,10-dihydroanthracene in storage 22 has a P y f 7 to 85% that can usually be easily raised to a purity of over 99% by a single recrystallization in a crystallizer 42 from a solvent obtained from storage I2. The crystals from a crystal separator 44, after being washed with solvent from storage I2, go to a dryer 46, whereas the mother liquor from separator 44 is recycled to the fractionator I8 to separate its constituents. From the dryer 46, the 9,10-dihydroanthracene having a purity of better than 99% goes to a storage 48. The 9,10-dihydroanthracene can easily be dehydrogenated in a dehydrogenation apparatus 5ll'by known means, for example, by treatment with sulphur, to yield anthracene of over 99% purity. Alternatively, this substantially pure 9,10-dihydroanthracene in storage 48 can go through an oxidation step in an oxidizer 54 by known means, for example, by oxidation with chromic acid to produce anthraquinone in storage 56 having a purity of over 99%, that is suitable for use in the dye industry. The 9,10-dihydroanthracene in storage 22 can obviously be dehydrogenated to anthracene or oxidized to anthraquinone. However, where highly purified products are required, it is preferred to purify the 9,10-dihydroanthracene rather than to purify either of the conversion products.

Referring to the flow sheet of Figure 2, the crude anthracene from storage I02, including the recycled still residue from a still I I33, is transferred to a hydrogenation apparatus I04, and is therein admixed with a metal sulphide dehydrogenation catalyst from storage I06, the mixture being heated under the pressure of hydrogen from storage I08 for a period sufilcient to convert a major portion of the anthracene content of the mixture to 9,10-dihydroanthracene. This operation is similar to the hydrogenation of anthracene as described withreference to Figure 1. hydrogenated product flows from hydrogenation Theapparatus I04 to a catalyst'separator III]; where the insoluble catalyst is filterdioriotherwise separated'from the hot, liquid product, the separated catalyst being recycled to storage 16- for further use, whereas the hydrogenated product flows to a fractionator II2 for separation of its constituents, preferably at a subatmospheric pressure, to reduce both the dehydrogenation of 9,10-dihydroanthracene to anthracene. and tar formation. From a very crude starting material the usual four fractions from a fractionator 2 are forerunnings to storage H4, the 9,10-dihydroanthracene product to storage II6, a phenanth'renecarbazole mixture to storage 8V and the still residue to storage 120. The forerunningspand still residue can be further fractionated or otherwise treated to separate therefrom other minor constituent-s present with the crude anthracene. It is also possible, simply to distill off any forerunnings with the 9,10-dihydroanthracene and to purify the 9,10-dihydroanthracene found therein. The "still residue now comprising carbazole, phenanthrene, etc., is then solvent extracted as described.

Where the anthracene is presentin a closeboiling tar fraction or where the impure anthracene is derived otherwise than from; tar, it is possible, after a hydrogenation step to distill off the 9,10-dihydroanthr-acene substantially unchanged at ordinary pressures The other constituents remain as still residue. Relatively pure 9,10-dihydroanthracene can be distilled at'ordinary pressures without change; However, when crude, anthracene as an anthracene oil or anthracene cake is sufiiciently hydrogenatedand then distilled at atmospheric pressure, the yield of 9,10-dihydroanth nacene is low. Something that is present in the crude product tends to bring about the dehydrogenation of the. 19,10-dihydroanthracene to anthracene. It was found that when the 9,10-dihydroanthracene was distilled at reduced pressures, for example, at about50 mm. substantialy no dehydrogenation resulted.

However, where carbazole is present with the 9,10-dihydroanthracene and is also to be distilled, it is preferred for carbazole distillation to increase the pressure to over 150 mm; after the 9,10-dihydroanthracene has been removed at about 50 .mm. Distillation of'the hydrogenated anthracene cake at 150 mm, causes some dehydrogenation of the 9,10-dihydroanthracene. The

reason for the use of twodiiferent pressures is that at 50 .mm. the boiling temperature of the carbazole is lower than its meltingpoint. There fore, instead of distilling over, the carbazole sublimes and. thus tends to plug thedisti-llation-apparatus. I

The phenanthrene-carbazole mixture from storage II 8 flows to a ph'enanthreneextractor I22, wherein solvent from storage I24 selectively dissolves phenanthrene from'carbazole, the ex-" tract flowing to a still I26 for separation of the solvent that is returned to storage I24, the residue flowing to a storage tank I28. The phenanthrene product in tank I 28 usually has a purity of '7 0% to The solvent here as for the operation described in Figure 1 can be an aliphatic solvent or even a naphthene, for example, a pctroleum solvent, an alcohol or a naphthene such as cyclohexane. From the extractor I22 the carbazole goes to a crystallizer I30- for further purification. l

At this point in the process system the separated products are essentially the same as are those obtained in Figure 1. 'I'l'iey-are similarly enemas" disposed tor as :zregards tiie forerunni-ngs' in storage,I I4., the still residue .in storage; I20, and the phenanthrene in storage I28; .The carbazolein a cry'stallizer [30 and the 9,1'0-dihydroanthracene in a storage tank IIB are. essentially'the same products as are obtained infFigure l, and. they are purified in like'mann'er;

Thus, the carbaZo-l'e in a crystallizer I'30i's crysa purity of '7.5% to 85% thatis raised in a crystallizer I42 by treatment with a solvent from tank I24, the crystals in the separator gI44 being Washed with fresh solvent from tank I24 and then being dried in a dryer I 46 to give a 9,10-dihydroanthracene stored in tank I48 having a.

purity of over-99%. The mother liquor frornthe separator I44 goes to astill I59 for separation of solventrthat flows-to solvent storage I 24, the;

residue flowing to the fractionator I I2 for reworking.

The substantially pure 9,10-dih-ydr-oanth1ia'cene in tank I48 can alternatively ;go through a de hydrogenation step in ar-dehydrogenation apparatus I52 for conversion to anthracenestored in tank I54 or through an; oxidation step-inaan thraquinone stored in a tank -I58.:by the-methods described for Figure l.

The present invention is one ofgreat econonric importance because of the. high recovery and purity of the anthracene recovered. ltxhasfbeen demonstrated that at .press'u'resaof from 2Qfito 100 atmospheres and usually within the rangei'of 40 to 60 atmospheres, the =-anthracene.presentjeven in small proportions in a crude product can be selectively hydrogenated to substantially ionly 9,10-dihydroanthracene. This mild, slow and selective hydrogenation. can be effected in less expensive low pressure equipment thaniis required by the prior art. Th'e proce'ss also leaves the carbazole and phenanthrene substantially unchanged. .-Furthermore,. when starting with a solid anthracene cake, :the, hydrogenated ;product therefrom contains a,-minimum*o'f::1iquefied, aromatic hydrogenated "material that would disoxidation apparatus 156 for conversion to ansolve the valuable carbazole and carry it away-in any subsequent solvent extraction step." With this hydrogenation process the recoverypf'carbazolehas been raisedappreciably-fromthermaximum heretoforeobtained by theprocessessof-the prior art. 7

The 9,IO-dihydroanthracene formed in the rseilective hydrogenation reaction and present in a complex, crude fraction possesses physicalipro'p- 1 erties that simplify not only its separationxbut also that of-the carbazole' andlphenanthrene from any crude-tar fraction. 'It'i's-a heat-stable prod uct 'Witha boiling point of 313 C; tha't is'sufiiciently belowthat ofcarba-Zole: and phenanthrene to permit separation by distillation of thegcrude material. As compared to anthracene, which forms flocculent crystals-that occludeim-pu'rities during their crystallization; the 9,1-l )-dihydroaii- J thracene forms crystals that are remarkably free of other impurities. For example, the first-separated product has a purity of to which by as'ingle recrystallization from appropriate solvents canbe. purified in 7 good yields. to 9,10-dihydroanthracene, having apurityof over 99 The ability of remove the 9 ,10-dihydroanthracene efficiently from the crude hydrogenated product maksit possible to. obtain higher yields-of purer carbazole and phenanthrene, and also simplifies their purification, where required, to the pure products. Additionally, it simplifies the concentration and preparation of. the minor constituents such as the acenaphthenafluorcne, etc. By hydrogenating theanthraceneto -9,1 0-di- .hydroanthracene, the solvent selectivity of the product is changed remarkably and advantageously for separation from .crudes. .The 9,10-

dihydroanthracene is relatively soluble so- I calledaliphatic type. solvents such as petroleum solvents, andalcohols, as well as naphthenes, that permit a rapid, sharp separation from carbazole- Anthracene, on the other hand, .is soluble along with carbazole in aromatic solvents, thus, making separation therebetween difficult.

-The disclosed methods for handling the .9,10-

dihydroanthracene are of course generally applicable to the handling of hydrogenated crude anthracene, regardlessof thenature or source of the original crude or of the conditions such as temperature, pressure, catalyst,. time, etc; -:em-.

ployed for hydrogenatinga crude anthracene.

The high purity of the :9,IO-dihydroanthracene makes it. an easy matter to use known reactions to convert it'to anthracene and anthraquinoneoi equally high purity. It is also apreferred matei rialfor further hydrogenation to the higherhy drides. :In the production :of anthraquinone suit able for use in the dye. industry, the usual pure anthracene of commerce :is treated, for eX- ample, -vvith chromic acid toproduce anthraquinone. HoweVergbecause of the impurities present V in theoriginal anthracene, the resultingiproduct ,must be treated with between five and ten times its Weight of concentrated sulphuric acid, followed by dilution andsublimation to obtain a suitable, pure. anthraquinone. process steps are eliminated, where the'9,10-dihydroanthracene is directly oxidized .to'anthra quinone or is firstdehydrogenatedto anthracene and the anthraceneoxidized to anthraquinone. In this connection a reaction velocity study showed thatthe 9,10-dihydroanthracene oxidized :to anthraquinone in an'aquecussolution of .chr.o-'

micacidnearlytwice asrapidly as .did anthrae cone.

of the results obtainable inthe practice e f-the .present invention. All quantitiesrare in .partsby weight unless otherwisedesignated. I

Examplcl '7 According to the procedure described with reference to "Figure 1, .there was' hydrogenated in a shaking autoclave for five hoursat 300-'.C.:and

and make its purificatiomdifficult asWellies (Jon'- taminating the carbazole and ithephenahthrehe' under an average:hydrogen'pressure 012600 pfs. i. (about 41 atmospheres), a mixture 'o'f :90 'parts NiS catalyst,-900,parts anthracene cake an'dYIl-O wparts recycle :stiillre'sidue 'fromaprevious' run.

The anthracenecake analyzed 33.2% .anthra'ce'ne and- 18.9% carbazolepthe remainder being phenanthrene :and other materials boiling in the anthraceneoilf range lIhe'still residue analyzed .21 anthracene andi'29 carb azole. lThe hydro These expensive The following specific examples are. illustrative genated cake was extracted with Skelly Solve B, a commercial type of refined petroleum solvent (B. P. 60-71 C.) to dissolve out 9,10-dihydroanthracene and phenanthrene. The remaining cake was dissolved in xylene and the carbazole recovered therefrom in a 63.3% yield of a product having a purity of 91.8%. The Skelly Solve solution was fractionated at 42 mm. pressure, a fluorene cut (B. P. 178-190 C.) and the 9,10-dihydroanthracene out (B. P. 190-200 C.) distilling over. The still residue comprised about 70% phenanthrene, which on treatment with ethyl alcohol yielded a phenanthrene of 85-90% purity. The 9,10-dihydroanthracene cut (78.8% purity) represented 77.8% of the theoretical recovery. A single recrystallization from ethyl alcohol yielded 9,10-dihydroanthracene having a purity of over 99%.

Comparison runs were made in a manner similar to that hereinabove described with the same crude anthracene cake and the same quantity of NiS catalyst. However, the temperature, time, and hydrogen pressure were each varied to determine the effect thereof on the yield of 9,10- dihydroanthracene from the same crude anthracene cake. The purity of all products was raised to over 99% 9,10-dihydroanthracene upon recrystallization. The results of the runs are tabulated below.

Comparing runs 1 and 2, the change in temperature from 300 C. to 275 C. appears to be beneficial in that there is an increase in the yield and purity of the 9,10-dihydroanthracene. Comparing runs 1 and 3, the change in time from 5 hours to 'hours while not beneficial brings about only a small decrease in yield of 9,10-dihydroanthracene. This is very important, for in the prior art, such excess hydrogenation time reduced the yields appreciably. In run 4 at 90-100 atmospheres there is a further small decrease in yield of 9,10-dihydroanthracene although the product is somewhat purer.

Yet another run was made in a manner as hereinabove described with a somewhat purer anthracene cake comprising 59.4% anthracene, and 20.3% carbazole. The five-hour run with 10% NiS catalyst was made at 300 C. and at a pressure of 600 lbs. per square inch with 700 lbs. per square inch maximum. The carbazole (92.0% pure) recovery was 80.6% of theoretical, while the 9,10-dihydroanthracene (99.2% pure) was 78.2% of theoretical. Both yields and purity were improved over those obtained with a cruder anthracene cake.

Example 2 To determine the yields and purity of anthracene obtainable by dehydrogenating 9,10- dihydroanthracene with sulphur, there were heated 50 grams 9,10-dihydroanthracene (99.5% pure) with a molecular equivalent of sulphur (9 grams) for one hour at 225 C. The contents of the flask were extracted once with 600 cc. hot xylene and the formed crystals washed with 10 200 cc. cold xylene. Three more batches of 50 grams 9,10-dihydroanthracene were dehydrogenated with sulphur as previously described, the anthracene in each instance bein extracted with the same recycled xylene. From the four runs there was recovered 91.3% anthracene (99.7% pure). The xylene was distilled and the remaining 7.3% anthracene pure) recovered to give an overall recovery of 98.6% of the theoretical.

Example 3 To determine the yields and purity of anthraquinone obtainable by oxidizing 9,10-dihydroanthracene with chromic acid there were added to a flask grams pulverized 9,10-dihydroanthracene (over 99% pure) produced in accordance with this process and 350 m1. of 72.4% Na2C1'2O7 solution. The flask was heated to 100 C. with stirring of contents and a solution of 375 ml. of concentrated sulphuric acid in one liter of water added through a dropping funnel. The acid was added over a. period of two hours and the oxidation continued for an additional eight hours. The contents of the flask were filtered, the filter cake washed, dried and then extracted with xylene. Without recycling the xylene for further recovery of product there was obtained an 86.8% yield of theoretical of anthraquinone (melting 282- 283 C.) that was suitable for use in dye manufacture.

Example 4 According to the procedure described with reference to Figure 2, there Was hydrogenated for five hours at 300 C. and under a hydrogen pressure maintained between 600 and 800 p. s. 1. (about 41 to 55 atmospheres), a mixture of 50 parts NiS catalyst, 500 parts anthracene cake and 50 parts recycle still residue from a previous run. The anthracene cake and still residue analyzed about the same as in Example 1. A portion of the hydrogenated product after separating the N18 catalyst was distilled at mm. pressure to distill over 9,10-dihydroanthracene, that was recovered from petroleum solvent in a 57% yield of 9,10-dihydroanthracene (99 plus percent pure). The other portion of the hydrogenated product that was distilled at 20 mm. pressure gave a 75.3% yield of 9,10-dihydroanthracene (99 plus percent pure). The decreased yield of about 18% at the higher pressure was believed due to an impurity induced dehydrogenation of the 9,10-dihydroanthracene to anthracene. The combined still residue comprising a carbazolephenanthrene cut was extracted with petroleum solvent to separate phenanthrene. The remaining carbazole product when treated with xylene was recovered as carbazole (91.% pure) in a 56.8% yield of theory.

The invention as hereinabove set forth is embodied in particular form and manner but may be variously embodied within the scope of the claims hereinafter made.

We claim:

1. A process for refining anthracene cake con-, taining anthracene, carbazole and phenanthrene comprising: hydrogenating anthracene cake in the presence of metallic sulfide hydrogenation catalyst at a temperature of 275 to 300 C. and a pressure of 40 to 60 atmospheres for a time period to obtain a maximum conversion of anthracene to 9,10-dihydroanthracene, filtering catalyst from the hydrogenation products, distilling hydrogenation products to separate 9,10- dihydroanthracene and phenanthrene and exwith aloW boiling aromatic hydrocarbonj 2L A'process for refining. anthracene cake containing anthracene, carbazole and phenanth'rene comprisingi hydrogenating anthracene cake in thepresence of a metallic sulfide hydrogenation c a taly st at temperatures of 275 to 300 G and pressures offlO to fioatrnospheres fora period 1 of time to obtain amaximum yield'of anthracene to 9,l0 -dihydroanthracene, filtering thecatalyst from the hydrogenation products, distilling the hydrogenation products under a high vacuum pressure 1 to separate 9,10-diliydroanthracene,

" continuing-the distillation under a reduced vacuu'rnpressure to separate phen'anthrene, and eX- 'tracting carbazole from the'distillation'residue with an aromatic solvent.

process forrefining'anthracene'cake containing anthracene, carbazole and phenanthrene comprising: hydrogenatin'g anthracene cake in thepres'ence of a metallic sulfide hydrogenation catalyst at" a temperature of 275 to" 300 C. and a' pres'sure'of 40 to 60 atmospheres i'or a time period to obtain a maximum conversion of anthracene to 9,10 dihydroanthracene{ filtering the catalyst from the' hydrogenation products and] distilling the hydrogenation products under raj comparatively high vacuum pressure to recover a comparatively pure QJO-dihydroanthracene. 4. A-process' for refinirig anthracene cak'econtaining anthracene, carba zole and phenanthrene comprising: hydrogenating anthracene cake in the presence of a metallic sulfide hydrogenation "catalyst at a temperature of 275 -to'3Q0" C. and

a pressure ,ofO: to 60' atmospheres for, a" time period to. obtain a maximum yield of anthracene to9,10 dihydroanthracene, filtering the hydrogenation products to remove catalyst, distilling the hydrogenation" products to separate .phen- 'anthren'e' therefrom and extracting carbazol'e 'fromthe' hydrogenation residue by solvent -extraction. V V

'5. A'process for refining anthracenecake containing anthracene, carbazole and phenanthrene comprising: hydrogenating anthracene cake in 'the'presence of a metallic sulfide hydrogenation catalyst'a'ta' temperature of 275 to 300 C. and a'pressureof 40 to 60 atmospheres for a" time period'to obtain a maximum yield of 9,10-dihydroan'thracene; separating catalyst from the hydrogenation products, distilling under acomparatively high va-cuum'the' hydrogenation products to separate 9,10;dihydroanthraceneas an overhead product, and continuing the distillation under a reduced vacuum pressure to separate the ph'enanthrene from the hydrogenation products. 0 1}, processior refining anthracene ceremontaining anthracene, carbazole and phenanthrene comprising: hydrogenating anthracene cake in the presence of a metallic sulfide hydrogenation catalyst at a temperature of 275 to 300 C and a droanthracene, separating catalyst from the hycatalyst at a temperature of 275 to 300 C'Land a pressure of 40 to 60'atmospheres for a time period to obtain a maximum yield of-'9,10-dihydroanthracene, separating catalyst 'from the hydrogen'ation' products, distilling under a comparatively high vacuum the hydrogenation products to separate 9,10-dihydroanthrace'ne as'an overhead product, and dehydrogenating the 9,10- dihydroanthracene with sulfur to recover apurified anthracene. f

8', A process for refining'anthracene cake containing anthracene, carbazole, and phenanthrene comprising: hydrogenating anthracene cake in the presence of a metallic sulfide hydrogenation catalyst at a temperatureof 275 to 300 C. and a pressure of 40 to ,60 atmospheresfor a time period to obtain a maximum yield of 9,10 -dihydrogenation products, distilling under a comparatively high vacuum the hydrogenation products to separate 9,10-dihydroanthraceneas an overhead product, recrystallizing the 9,10-dihydroanthrac'ene with an aliphatic alcohol solvent, and dehydrogenating the recrystallized 1 product with sulfur to obtain a purified anthracene.

9. A process for refining anthracenei cake'containing anthracene, carbazole and phenanthrene comprising: hydrogenating anthracene cake in the presence of a metallic sulphide hydrogenation catalyst at a temperature 'of- 275 to 300 C. and a pressure of 40 to 60 at'mospheres'forv a time period to obtain a maximum yield'of 9,10- dihydroanthracene, separating the catalyst from the hydrogenation products, distilling the hydrogenation products under a vacuum to separate a 9,10-dihydroanthracene cut and a separate out REFERENCES CITED The following references ar'e'of reco rd in the file of this patent:

UNITED STATES PATENTS Number Name 1 h Date 1,591,712 Lewis July 6, 1926 1,897,798 Guthke Feb. 14,1933 1,939,224 Pretzsch Dec. 12, 1933 1,940,065 7 spannagel et a1. 'Dec, 19, 1933 1,965,956 Dunkel 81; a1." Jilly 10, 193% 1,972,157 Miller Sept. 4, 1934 1,999,738 Pier et al. -2 Apr. 30, 1935 FOREIGN PATENTS Number Country Date 7 687,957 France i May.5, 1930 733,704: France -2 July 18,1932 813,647 France Mar; '1, 1937 OTHER REFERENCES Padova, Annales de Chemie (8),19,432 (1910).

Prokopets, Chemical Abstracts, vol. 33,, page 1717 (1939). 

